JPH05257297A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and mechanical durability of the photosensitive layer of the electrophotographic sensitive body and to obtain good surface smoothness by including a binder resin made of a specified copolymer and a specified electric charge transfer material in the photosensitive layer. CONSTITUTION:The photosensitive layer contains the binder resin of the copolymer composed essentially of structural units each represented by formulae I or II in which each of R1 and R2 is H or an aryl or the like; each of R3-R6 is H or a halogen or the like; and each of l, m, p, and q is an integer of 1-4. The photosensitive layer contains also the charge transfer material represented by formula III in which Ar1 is a phenyl substituted by (R3)i or the like; each of Ar2 and Ar3 is a phenyl substituted by (R4)j or the like; Ar4, Ar5 is phenyl group substituted by (R5)k, each of R1 and R2 is a phenyl substituted by (R6)l or the like; R3 is an alkyl, a phenyl, or the like; each of R4-R6 is an alkyl, an alkoxy, or the like; each of i, k, and l is an integer of 0-5; and j is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
In particular, the present invention relates to an organic photoconductive electrophotographic photosensitive member, and further to film physical properties of a constituent layer of the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art In an electrophotographic copying machine of the Carlson method, after uniformly charging the surface of a photoconductor, the charge is erased imagewise by exposure to form an electrostatic latent image. Is developed with toner, and then the toner image is transferred and fixed on paper or the like.

On the other hand, the photoconductor is subjected to removal of adhered toner, charge removal, and surface cleaning, and is repeatedly used for a long period of time.

Therefore, as an electrophotographic photosensitive member, of course, electrophotographic characteristics such as good charging characteristics and sensitivity and small dark decay, as well as printing durability after repeated use, abrasion resistance,
It is also required to have good physical properties such as moisture resistance, and resistance (environmental resistance) to ozone generated during corona discharge and ultraviolet rays during exposure. Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide as a photosensitive layer main component has been widely used.

In recent years, as a photosensitive layer of an electrophotographic photoreceptor, a carrier generating function and a carrier transporting function are shared by different substances, and substances exhibiting respective functions are selected from a wide range according to desired characteristics, and sensitivity is increased. There is a trend toward putting organic photoreceptors with high durability into practical use.

Such a function-sharing type organic photoconductor has been used mainly for negative charging, and a thin carrier generating layer is provided on a support as described in JP-A-60-247647. The structure is such that a relatively thick carrier transport layer is provided.

As a binder used for such a photoreceptor, a bisphenol A type polycarbonate represented by the following structural formula exhibits good characteristics in terms of charging characteristics, sensitivity, residual potential and repetitive characteristics. Is well known.

[0008]

[Chemical 5]

However, as a result of investigations conducted by the present inventors, the bisphenol A-type polycarbonate has a high polymer crystallinity, so that its solution easily causes gelation.
It has a drawback that it becomes unusable in about a day. Further, when a film is formed by coating, crystalline polycarbonate is likely to be deposited on the surface of the film at the time of forming the coating film to form a convex portion, which causes tailing of the coating film to reduce the yield, or as a photoreceptor. The toner adheres to the convex portions during use and remains uncleaned, and image defects due to so-called poor cleaning are likely to occur.

An electrophotographic photosensitive member using the above bisphenol A type polycarbonate as a binder resin is
When it is used as a photoconductor of an electrophotographic copying machine, it has the drawbacks that it is scratched by a magnetic brush or a cleaning blade, the surface of the photosensitive layer is scratched, and the photosensitive layer is gradually abraded.

On the other hand, since the high image quality and good copying workability depend on the quality of the smooth and uniform surface property of the photosensitive member having a uniform thickness, a coating composition for forming the constituent layer of the photosensitive member coating constituent layer surface. Alternatively, the trouble of the film surface such as citrus cortex, pinholes, coating streaks, and cracks (solvent cracks) caused by coating and drying is a serious problem in terms of copying characteristics and production technology.

In response to the above-mentioned problems, introduction of a bulky group on the carbon between the phenylene rings (JP-A-60-1720).
45), and the introduction of a substituent having fluorine (Japanese Patent Laid-Open No. 63-6454).
No. 4), substitution of an alkyl group or a halogen atom to the phenylene ring (JP-A-63-148263), or a copolymer of monomers in which both phenylene rings are substituted with a phenyl group or a cyclohexyl group (JP-A-1-269942). No. 1-26943), or using bisphenol Z-type polycarbonate in combination with distyryl as a charge-transporting substance (Japanese Patent Laid-Open No. 64-32265), but still sufficient surface strength and surface smoothness have been proposed. However, it has poor resistance to abrasion and cracking, causes deterioration in image quality during repeated use, and has a problem in that sensitivity is reduced due to reduction in film thickness due to abrasion.

[0013]

OBJECTS OF THE INVENTION The object of the present invention is high sensitivity, high mechanical durability of the electrophotographic photosensitive layer, good surface smoothness, good crack resistance and ozone resistance, and poor image quality. , And to provide an electrophotographic photosensitive member with less deterioration in sensitivity.

[0014]

The object of the present invention is to provide an electrophotographic photoreceptor having a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin on a conductive substrate, wherein the photosensitive layer is a binder resin represented by the following general formula: It contains a copolymer compound having a structural unit represented by [B ₁ ] and a structural unit represented by the following general formula [B ₂ ] as main components, and a charge transporting substance represented by the following general formula [T]. And an electrophotographic photosensitive member.

[0015]

[Chemical 6]

[Wherein R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, etc.), R ₁ and It represents a cyclic hydrocarbon residue of C ₄ -C ₁₀ formed by R _2.

R ₃ , R ₄ R ₅ and R ₆ are each a hydrogen atom,
Halogen atom (for example, atom such as chlorine, nitrogen, iodine), substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, C ₄
To C ₁₀ cyclic hydrocarbon residue, substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group). l, m,
p and q are integers of 1 to 4.

A preferred embodiment is an electrophotographic photoreceptor containing a copolymer compound in which the repeating structural units of the above formulas [B ₁ ] and [B ₂ ] are as follows.

[0019]

[Chemical 7]

The degree of polymerization of the copolymer of the present invention is 10 to 500.
It is 0, preferably 50 to 1000. In the present invention, the general formula [B
₁ ] and a copolymer containing the general formula [B ₂ ] in the structural composition are used as a binder resin, the film has excellent physical properties, excellent electrophotographic properties such as charge retention and sensitivity residual potential, and is repeatedly used. It is possible to produce an electrophotographic photosensitive member that exhibits stable characteristics with little fatigue deterioration even at times.

Further, if necessary, other monomers can be mixed and used within a range that does not hinder the intended function and effect. The mixing ratio at this time is preferably 50 wt /% or less.

The copolymer compound of the present invention has the following (I) and
It is easily synthesized by a conventional method using a phenolic compound selected from (II).

[0023]

[Chemical 8]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
l, m, p and q are the same as those shown in the above general formulas [B ₁ ] and [B ₂ ].

The method for producing the copolymer compound of the present invention is specifically as follows. The phenolic compound is added to the phenol compound in the presence of an inert solvent such as methylene chloride or 1,2-dichloroethane as an acid acceptor. A method of adding pyridine or the like and reacting while introducing phosgene can be mentioned.

When an aqueous alkaline solution is used as the acid acceptor, the reaction rate can be improved by using a tertiary amine such as trimethylamine or triethylamine or a quaternary ammonium compound such as tetrabutylammonium chloride or benzyltributylammonium bromide as a catalyst. Increase.

If desired, a monovalent phenol such as phenol or pt-butylphenol may coexist as a molecular weight regulator. The catalyst may be added from the beginning, or any method may be used, such as adding the catalyst after forming the oligomer to increase the molecular weight.

In the present invention, as a method of copolymerizing two or more phenolic compounds, (a) a method of first reacting two or more phenolic compounds with phosgene at the same time and copolymerizing (b) ) A method in which one is first reacted with phosgene, a certain amount of reaction is carried out, and then the other is added and polymerized (c) Any method such as a method of separately reacting with phosgene and polymerizing can be employed.

Specific examples of the structures represented by the general formulas [B ₁ ] and [B ₂ ] will be given below, but the present invention is not limited thereto.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

The following are examples of the copolymer compound having both structures, but the present invention is not limited thereto.

[0037]

[Table 1]

In the above table, the ratio of x and y in the copolymer compound (copolymerization ratio) is in the range of x: y = 95: 5 to 5:95, more preferably 95: 5 to 50:50. The range is.

When the ratio of y is 50% or more, the sensitivity and mechanical strength decrease, so that the ratio of y should be 50%.
The following is preferable.

Examples of binders that may be used in combination with the copolymer compound of the present invention used as the binder include the following.

(1) Polyester (2) Methacrylic resin (3) Acrylic resin (4) Polyvinyl chloride (5) Polyvinylidene chloride (6) Polystyrene (7) Polyvinyl acetate (8) Styrene copolymer resin (for example, styrene- Butadiene copolymer, styrene-methyl methacrylate copolymer, etc.) (9) Acrylonitrile-based copolymer resin (for example, vinylidene chloride-acrytronitrile copolymer, etc.) (10) Vinyl chloride-vinyl acetate copolymer Combined (11) Vinyl chloride-vinyl acetate-maleic anhydride copolymer (12) Silicone resin (13) Silicone-alkyd resin (14) Phenolic resin (for example, phenol-formaldehyde resin, cresol-formaldehyde resin, etc.) (15) Styrene-alkyd resin (16) Poly-N-vinylcarbazole (17) Polyvinyl butyral (18) Polyvinyl forma Le (19) polyhydroxystyrene These binders may be used together in a co-critical condition compounds according to the present invention alone or as a mixture of two or more.

Next, the charge transport material (CTM) represented by the general formula [T] will be described.

[0043]

[Chemical 15]

In the formula, Ar ₁ is a phenyl group substituted with (R ₃ ) i, _three groups which are substituted or unsubstituted; a condensed polycyclic hydrocarbon group, a heterocyclic group and a condensed polycyclic hetero group. Represents a ring group.

Ar ₂ and Ar ₃ are a phenyl group substituted with (R ₄ ) j, _three groups which are substituted or unsubstituted; a condensed polycyclic hydrocarbon group, a heterocyclic group, and a condensed polycyclic hetero group. Represents a ring group.

Ar ₄ and Ar ₅ are a phenyl group substituted by (R ₅ ) k, three groups which are substituted or unsubstituted; a condensed polycyclic hydrocarbon group, a heterocyclic group and a condensed polycyclic system. Represents a heterocyclic group.

R ₁ and R ₂ are a phenyl group substituted with (R ₆ ) l, three groups which are substituted or unsubstituted; a condensed polycyclic hydrocarbon group, a heterocyclic group and a condensed polycyclic system. It represents a heterocyclic group and may form a ring together with Ar ₄ and Ar ₅ . R ₃ is a substituted or unsubstituted alkyl group, phenyl group, alkoxy group, phenoxy group and cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, and further substituted or unsubstituted 6 Group: represents an alkylamino group, an arylamino group, an aralkylamino group, a cyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group.

R ₄ , R ₅ and R ₆ are the following four groups which are substituted or unsubstituted; alkyl group, phenyl group, alkoxy group, phenoxy group and cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group. , A nitro group, an amino group, and further six groups which are substituted or unsubstituted; an alkylamino group, an arylamino group, an aralkylamino group,
It represents a cyclic hydrocarbon group, a condensed polycyclic hydrogen group or a heterocyclic group.

I, k, and l represent integers of 0 to 5, and j is
It represents an integer of 0 to 4. Specific examples of the compound of the CTM of the present invention represented by the general formula [T] are shown below, but the invention is not limited thereto.

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19]

[0054]

[Chemical 20]

[0055]

[Chemical 21]

[0056]

[Chemical formula 22]

The CTM which can be used in combination in the present invention is not particularly limited, and examples thereof include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivative, styryl compound, hydrazone compound, pyrazoline derivative, amine derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative,
Examples include acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like.

The CTM used in the present invention is excellent in the ability to transport holes generated at the time of light irradiation to the support side, and is preferably a CTM suitable for combination with the organic pigment used in the present invention. In the photoconductor of the present invention, the organic pigments represented by the following representative examples are used as the charge generating substance (CGM).

(1) Azo pigments such as monoazo pigments, bisazo pigments, triazo pigments, metal complex salt azo pigments (2) Perylene pigments such as perylene anhydride, perylene imide (3) Anthraquinone derivatives, anthanthrone derivatives, dibenz Polycyclic quinone pigments such as pyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isoviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives. It is preferable to use an organic pigment such as a polycyclic quinone, a perylene pigment, or a phthalocyanine pigment. In particular, when the following fluorenone-based disazo pigments, fluorenylidene-based disazo pigments and polycyclic quinone pigments are used in the present invention, markedly improved effects are obtained in terms of sensitivity, durability and image quality.

The fluorenone type disazo pigment used in the present invention is represented by the following general formula [F ₁ ].

[0061]

[Chemical formula 23]

[In the formula, X ₁ and X ₂ each represent a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group or a substituted or unsubstituted amino group. p and q each represent an integer of 0, 1 or 2,
When p and q are 2, X ₁ and X ₂ may be the same or different groups.

A represents a group represented by the following general formula [F ₁ -1]. ]

[0064]

[Chemical formula 24]

[In the formula, Ar represents a fluorinated hydrocarbon group or an aromatic carbocyclic group having a substituent or an aromatic heterocyclic group.
Z represents a non-metal atom group necessary for forming a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle. ] M and n represent the integer of 0, 1 or 2, respectively. However, m and n are not 0 at the same time.

Specific examples of the fluorenone-based disazo pigment used in the present invention are shown below, but the invention is not limited thereto.

[0067]

[Chemical 25]

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

[Chemical 28]

The fluorenone disazo pigment represented by the above general formula [F ₁ ] used in the present invention can be easily synthesized by a known method, for example, the method of Japanese Patent Application No. 62-304862.

Next, the perylene pigment used in the present invention is represented by the following general formulas [P ₁ ] and [P ₂ ].

[0073]

[Chemical 29]

In the general formulas [P ₁ ] and [P ₂ ], Z is a substitution,
It represents a group of atoms necessary for forming an unsubstituted aromatic ring. ]
Preferred examples of Z mentioned above include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, a pyrazole ring, and an anthraquinone ring.
Particularly preferred are benzene ring and naphthalene ring.

Examples of the substituent of Z include alkyl, alkoxy, aryl, aryloxy, arylacyloxy, amino, carbamoyl, halogen, nitro and cyano groups. These perylene compounds were found to have a Bragg angle of 2θ of 6.3 ° ± 0.2 °, 12.5 ° ± 0.2 °, 25.4 ° ± 0.2 °, 27.2 ° in the X-ray diffraction spectrum for Cu-Kα radiation.
Those having a peak at ± 0.2 ° are preferable.

Specific examples of the compounds represented by the general formulas [P ₁ ] and [P ₂ ] are shown below, but the compounds are not limited to these.

[0077]

[Chemical 30]

The polycyclic quinone pigment used in the present invention is represented by the following general formulas [Q ₁ ] to [Q ₃ ].

[0079]

[Chemical 31]

[In each formula, X is a halogen atom, a nitro group,
Represents a cyano group, an acyl group, or a carboxy group, and n is 0
~ 4, m represents an integer of 0-6. Specific examples of the polycyclic quinone pigments represented by the above general formulas [Q ₁ ] to [Q ₃ ] used in the present invention are shown below, but the invention is not limited thereto.

Specific examples of compounds of the anthanthrone pigment represented by the general formula [Q ₁ ] are as follows.

[0082]

[Chemical 32]

Specific examples of the dibenzpyrenequinone pigment represented by the general formula [Q ₂ ] are as follows.

[0084]

[Chemical 33]

[0085]

[Chemical 34]

Specific examples of the compound of the pyranthrone pigment represented by the general formula [Q ₃ ] are as follows.

[0087]

[Chemical 35]

The above general formula [Q ₁ ] used in the present invention
The polycyclic quinone pigment represented by [Q ₃ ] can be easily synthesized by a known method.

As the metal-free phthalocyanine-based pigment that can be used in the present invention, photoconductive metal-free phthalocyanine and all of its derivatives can be used.
Type, β type, τ, τ'type, η, η'type, X type, and JP-A-62-62
The crystal form and its derivatives described in -103651 can be used. In particular, it is desirable to use the τ, X, K / R-X type. US Patent 3,35 for X-type metal-free phthalocyanine
7,989, and the τ-type metal-free phthalocyanine is described in JP-A-58-182639. The K / R-X type has a Bragg angle (2θ ± 0.2 degrees) with respect to the X-ray of CuKα, 1.541Å as disclosed in JP-A-62-103651.
It has major peaks at 7.7, 9.2, 16.8, 17.5, 22.4, and 28.8 degrees, and the peak intensity ratio of 16.8 degrees to 9.2 degrees is 0.8 to 1.0, and the peak of 28.8 degrees to 22.4 degrees. It is a phthalocyanine characterized by having an intensity ratio of 0.4 or more.

The oxytitanyl phthalocyanine used in the present invention is represented by the following general formula [TP].

[0091]

[Chemical 36]

[Wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent H, Cl or Br, and n, m, l and k are each independently 0.
Represents a number from 4 to 4. Among the oxytitanyl phthalocyanines used in the present invention, particularly preferred are those disclosed in JP-A-64
-17066 oxytitanyl phthalocyanine (Y-Ti
OPc) titanyl chlorophthalocyanine (TiOPcCl) and mixtures thereof.

As these oxytitanyl phthalocyanines, those having different crystal forms disclosed in the following patents are known. For example, JP-A-61-239248 and JP-A-62-6709
No. 43, No. 62-272272, No. 63-116158, No. 64-17066 and the like.

Examples of the dispersion medium of the organic pigment used in the present invention include hydrocarbons such as hexane, benzene, toluene, xylene, methylene chloride, methylene bromide, 1,2-dichloroethane, syn-tetrachloroethane, and cis. -1,2-dichloroethylene, 1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,2-dichloropropane,
Chloroform, bromoform, halogenated hydrocarbons such as chlorobenzene, acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, esters such as butyl acetate, methanol, ethanol, propanol, butanol, cyclohexanol, heptanol,
Alcohols such as ethylene glycol, methyl cellosolve, ethyl cellosolve, and cellosolve acetate, and derivatives thereof,
Ethers such as tetrahydrofuran, 1,4-dioxane, furan and furfural, acetals, amines such as pyridine and butylamine, diethylamine, ethylenediamine and isopropanolamine, nitrogen compounds such as amides such as N, N-dimethylformamide, and fatty acids. And phenols, sulfur such as carbon disulfide and triethyl phosphate, phosphorus compounds and the like.

In the present invention, the photosensitive layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential and reducing fatigue during repeated use.

Examples of the electron accepting substance which can be used here include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and 3-nitrophthalic anhydride. Acid, 4-nitrophthalic anhydride, pyromellitic dianhydride,
Mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bulmannyl, Dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone,
2,4,5,7-Tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9
-Fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid,
Examples include 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds having a high electron affinity. The addition ratio of the electron-accepting substance is a weight ratio of the organic pigment used in the present invention: the electron-accepting substance = 100: 0.01-200, preferably 100: 0.1-1.
00.

The addition ratio of the electron-accepting substance to such a layer is 100: 0.01 to 100, preferably 100: 0.1 to 50, by weight, total CTM: electron-accepting substance.

Further, organic amines can be added to the photosensitive layer of the present invention for the purpose of improving the charge generating function of CGM, and it is particularly preferable to add a secondary amine. These compounds are described in JP-A-59-218447 and JP-A-62-8160.

Further, in the photosensitive layer of the present invention, an antioxidant can be added for the purpose of preventing ozone deterioration. Typical specific examples of such an antioxidant are shown below, but the antioxidant is not limited thereto.

I-group; hindered phenols, II-group;
Paraphenylenediamines, III-group; hydroquinones, IV-group; organic sulfur compounds, V-group; organic phosphorus compounds.

These compounds are disclosed, for example, in JP-A-63-18354.

These compounds are known as antioxidants for rubbers, plastics, oils and fats, etc., and commercially available products can be easily obtained.

The antioxidant is added in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight, based on 100 parts by weight of CTM.

In addition, the photoreceptor of the present invention may further contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, and may also contain a dye for correcting color sensitivity.

If necessary, the electrophotographic photosensitive member of the present invention may be provided with an intermediate layer between the conductive substrate and the photosensitive layer.

Further, the intermediate layer functions as an adhesive layer or a blocking layer, and in addition to the binder resin,
For example, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, N-alkoxymethylated nylon, starch and the like are used.

As the electroconductive support used in the construction of the electrophotographic photosensitive member of the present invention, the following are mainly used, but the electroconductive support is not limited thereto.

1) A metal plate such as an aluminum plate or a stainless steel plate 2) A metal thin layer such as aluminum, palladium or gold provided on a support such as paper or a plastic film by laminating or vapor deposition 3) Paper or plastic A support such as a film provided with a layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide by coating or vapor deposition. The photoreceptor of the present invention is shown in FIGS. 1 (1) and 1 (2). Thus, the photosensitive layer 4 is provided on the conductive support 1 by a laminate of CGL2 containing CGM as a main component and CTL3 containing CTM according to the present invention as a main component. As shown in (3) and (4) of the figure, the photosensitive layer 4 is an intermediate layer 5 provided on the conductive support 1.
You may provide through. Thus, when the photosensitive layer 4 has a two-layer structure, an electrophotographic photosensitive member having the best electrophotographic characteristics can be obtained. Further, in the present invention, FIG.
Further, as shown in (6), the photosensitive layer 4 in which the particulate CGM 7 is dispersed in the layer 6 containing CTM as a main component is provided directly on the conductive support 1 or via the intermediate layer 5. May be.

Further, a protective layer 8 may be provided on the photosensitive layer 4 if necessary.

Here, when the photosensitive layer 4 has a two-layer structure, CG
Which of L2 and CTL3 is to be the upper layer is determined by whether the charging polarity is positive or negative. That is, in the case of forming the negative charging type photosensitive layer, it is advantageous to use CTL 3 as the upper layer, because CTM in the CTL 3 is a substance having a high hole transporting ability.

In addition, CGL 2 which constitutes the photosensitive layer 4 having a two-layer structure
Can be formed by the following method directly or on the conductive support 1 or CTL 3 with an intermediate layer such as an adhesive layer or a blocking layer provided if necessary.

(1) Vacuum evaporation method (2) Method of applying a solution in which CGM is dissolved in a suitable solvent (3) CGM is made into fine particles in a dispersion medium by a ball mill, sand grinder or the like and, if necessary, a binder. A method of applying a dispersion obtained by mixing and dispersing with.

That is, specifically, a vapor deposition method such as vacuum deposition, sputtering, or CVD, or a coating method such as dipping, spraying, blade, or roll method is arbitrarily used.

The thickness of the CGL2 thus formed is
0.01 μm to 5 μm is preferable, and 0.05 is more preferable.
μm to 3 μm.

The thickness of CTL 3 can be changed if necessary, but is usually preferably 5 μm to 30 μm. This CT
The composition ratio in L3 is preferably 0.1 to 5 parts by weight of the binder with respect to 1 part by weight of the CTM of the present invention, but when forming the photosensitive layer 4 in which fine particulate CGM is dispersed, CGM is used.
It is preferable to use the binder in an amount of 5 parts by weight or less with respect to 1 part by weight.

When the CGL is a dispersion type in the binder, 5 parts of the binder is added to 1 part by weight of the CGM.
It is preferably used in the range of not more than parts by weight. The photoconductor of the present invention has the above-mentioned structure and is excellent in charging property, sensitivity property, and image forming property, as will be apparent from the examples described later. In particular, even when it is subjected to a repetitive transfer type electrophotographic method, it has little fatigue deterioration and excellent durability.

[0117]

EXAMPLES Examples of the present invention will be specifically described below.
This does not limit the embodiments of the present invention.

Example 1 30 g of polyamide resin CM-8000 (manufactured by Toray Industries, Inc.) was added to methanol.
The mixture was put into a mixed solvent of 900 ml and 1-butanol (manufactured by Kanto Chemical Co., Inc.) 100 ml, and dissolved by heating at 50 ° C. Outer diameter using this liquid
It was applied by dipping onto an aluminum drum having a length of 80 mm and a length of 355.5 mm to form an intermediate layer having a thickness of 0.5 μm.

Next, 5 g of polyvinyl butyral resin S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.) was added to methyl ethyl ketone 7
100 ml, cyclohexanone was dissolved in a mixed solvent of (manufactured by Kanto Chemical Co., Inc.) 300 ml, which was mixed with F ₁ -23 10 g, it was dispersed for 10 hours using a sand mill. This solution was applied onto the intermediate layer by dip coating to form a charge generation layer having a thickness of 0.3 μm.

Next, 200 g of T-17 and 200 g of B-1 (x: y = 80: 20) as a CTL binder were dissolved in 1000 ml of 1,2-dichloroethane. After dip coating on the charge generation layer using this solution, it was dried at 100 ° C for 1 hour and
An m-thick charge transport layer was formed. Thus, a laminated electrophotographic photosensitive member including the intermediate layer, the charge generation layer and the charge transport layer was obtained.

Example 2 A laminated electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that C-18 was used as CTM.

Example 3 A laminated electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that CTM was changed to T-9.

Example 4 The formation of the intermediate layer was performed in the same manner as in Example 1.

Next, 10 g of polyvinyl butyral resin S-REC BX-1 was dissolved in 1000 ml of 1,2-dichloroethane,
CGM P-150g is mixed with this, and it is 20 using a sand mill.
Time dispersed. This solution was applied onto the intermediate layer by dip coating to form a 1.0 μm thick charge generation layer.

Next, CTM is added to T-13 and CTL binder is added to B.
A charge transport layer was formed in the same manner as in Example 1 except that the charge transport layer was changed to −2 (x: y = 75: 25) to obtain a laminated electrophotographic photoreceptor.

Example 5 The formation of the intermediate layer was performed in the same manner as in Example 1.

Next, polycarbonate resin Iupilon Z-
200 g (manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 1,000 ml of 1,2-dichloroethane (manufactured by Kanto Chemical Co., Ltd.), and CGM Q _1-3
20 g was mixed and dispersed using a sand mill for 24 hours. Using this solution, the intermediate layer was applied by dip coating to form a charge generation layer having a thickness of 1.0 μm.

Then, a charge transport layer was formed in the same manner as in Example 1 except that CTM was changed to T-19 and B-7 (x: y = 85: 15) was used as the CTL binder, and then laminated electrophotography was performed. A photoconductor was obtained.

Example 6 The intermediate layer was formed in the same manner as in Example 1.

Next, silicone resin KR-5240 (solid content 20
%) (Manufactured by Shin-Etsu Chemical Co., Ltd.) 100 g of methyl ethyl ketone 1000 ml
20 g of Y-type oxytitanium phthalocyanine (Y-TiOPc) was mixed and dispersed in a sand mill for 4 hours. By dip coating on the intermediate layer using this liquid,
A charge generation layer having a thickness of 0.5 μm was formed.

Next, a charge transport layer was formed in the same manner as in Example 1 except that CTM was changed to T-3 and the CTL binder was changed to B-12 (x: y = 70: 30), and then laminated electrophotography was performed. A photoconductor was obtained.

Example 7 200 g of CTM and B-5 as CTL binder
200 g of (x: y = 80: 20) was dissolved in 1000 ml of 1,2-dichloroethane. Using this solution, dip coating on an aluminum drum with an outer diameter of 80 mm and a length of 355.5 mm, and then at 100 ° C for 1
After drying for an hour, a charge transport layer having a thickness of 20 μm was formed.

Next, as a CGL binder, B-5 (x:
(Y = 80: 20) 200 g was dissolved in 1000 ml of 1,2-dichloroethane, and Q ₁ -360 g as CGM was mixed and dispersed for 24 hours using a sand mill. Furthermore, T as CTM in this liquid
-11 150 g was dissolved to obtain a coating solution. After spray coating on the charge transport layer using this solution,
After drying for an hour, a charge generation layer having a thickness of 5 μm was formed. Thus, a laminated electrophotographic photosensitive member including the charge transport layer and the charge generating layer was obtained.

[0134] except for changing the Comparative Example 1 CTL binder B ₁ -1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1.

[0135] An electrophotographic photosensitive member was prepared except for changing the Comparative Example 2 CTL binder B ₁ -7 in the same manner as in Example 1.

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that CTL was changed to the structural formula C-1.

[0137]

[Chemical 37]

—Evaluation of Electrophotographic Photoreceptors— The photoreceptors of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as “U-Bi”.
x3035 ”(manufactured by Konica Corporation), a 100,000-copy actual copying test was performed, and the presence or absence of image defects during the actual copying test, the change in surface potential before and after the actual copying test, and the film thickness loss amount were examined.

Black paper potential V _b : Surface potential for original with reflection density of 1.3 White paper potential V _w : Surface potential for original with reflection density of 0.0 Residual potential V _r : Surface potential after static elimination. "U-Bix3035" (manufactured by Konica) (equipped with a semiconductor laser light source)
_The crid voltage is adjusted so that _b becomes −700 ± 10 (V), the potential of the exposed surface when 0.7 mW of light is irradiated is set to V _w, and reverse development is performed with a developing bias of −600 (V). A similar live-action test was conducted.

Further, the photoconductor of Example 7 was changed to "U-Bix30".
35 ”(manufactured by Konica Corporation) was installed in a modified machine in which the polarity of transfer was changed to positive, and the same live-action test was conducted.

Regarding the film wear due to the friction on the surface, the film thickness of the photoconductor was measured after 100,000 copies and compared with the initial stage.

Regarding the cracks, the photoconductor was subjected to "U-Bi
x3035 "(made by Konica) drum cartridge,
With the cleaning roller pressed onto the photoconductor
It was left to stand in a constant temperature bath at 50 ° C for 1000 hours, and it was examined whether cracks were generated at one time.

The results are shown in the table below.

[0144]

[Table 2]

[0145]

EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention has excellent electrophotographic performance, has little change in characteristics even after repeated use, and has excellent crack resistance and abrasion resistance. Have.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing layers of an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Conductive Support 2 Charge Generation Layer (CGL) 3 Charge Transport Layer (CTL) 4 Photosensitive Layer 5 Intermediate Layer 6 Layer Containing Charge Transport Material 7 Charge Generation Material (CGM) 8 Protective Layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiaki Takei 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica Stock Company

Claims (3)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin on a conductive substrate, wherein the photosensitive layer is represented by the following general formula [B ₁ ] as a binder resin. An electrophotographic photograph containing a structural unit and a copolymer compound having a structural unit represented by the following general formula [B ₂ ] as a main component and a charge transporting substance represented by the following general formula [T]. Photoconductor. [Chemical 1] [In the formula, R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, R ₁ and R ₂
In it represents a cyclic hydrocarbon ring residues C ₄ -C ₁₀ formed.
R ₃ , R ₄ R ₅ and R ₆ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and C ₄ to
It represents a C ₁₀ cyclic hydrocarbon residue and a substituted or unsubstituted aryl group. l, m, p, and q are integers of 1 to 4. ] [Chemical 2] [In the formula, Ar ₁ is a phenyl group substituted by (R ₃ ) i, substituted or unsubstituted three groups described below; a condensed polycyclic hydrocarbon group, a heterocyclic group, and a condensed polycyclic heterocycle. Represents a group. Ar
₂ and Ar ₃ are phenyl groups substituted with (R ₄ ) j,
Substituting or non-substituted, the following three groups; a condensed polycyclic hydrocarbon group, a heterocyclic group, and a condensed polycyclic heterocyclic group. Ar ₄ and Ar ₅ are a phenyl group substituted with (R ₅ ) k, substituted or unsubstituted three groups described below; a condensed polycyclic hydrocarbon group,
It represents a heterocyclic group or a condensed polycyclic heterocyclic group. R ₁ and R ₂ are
(R ₆ ) l-substituted phenyl group, substituted or unsubstituted three groups described below; a condensed polycyclic hydrocarbon group, a heterocyclic group, a condensed polycyclic heterocyclic group, and Ar ₄ and A ring may be formed in cooperation with Ar ₅ . R ₃ is a substituted or unsubstituted alkyl group, phenyl group, alkoxy group, phenoxy group and cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, and further substituted or unsubstituted 6 Group: represents an alkylamino group, an arylamino group, an aralkylamino group, a cyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group. R ₄ , R ₅ and R ₆ are the following four groups which are substituted or unsubstituted; alkyl group, phenyl group, alkoxy group, phenoxy group and cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group. , An amino group, and further six groups which are substituted or unsubstituted; an alkylamino group, an arylamino group, an aralkylamino group,
It represents a cyclic hydrocarbon group, a condensed polycyclic hydrogen group or a heterocyclic group.
i, k, and l represent the integer of 0-5, and j represents the integer of 0-4. ] 2. The general formula [B ₂ ] is 2. The electrophotographic photosensitive member according to claim 1, which is a structural unit of 3. The general formula [B ₁ ] is represented by: The electrophotographic photosensitive member according to claim 2, wherein